| Description: | This article discusses four-coordinate Mo(II). Abstract: The reduction of [(tBu3SiO)2MoCI]2 (22) provided the cyclometalated derivative, (silox)2HMoMo(k-O,C-OSitBu2CMe2CH2)(silox) (3), and alkylation of 22 with MeMgBr afforded [(tBu3SiO)2MoCH3]2 (42). The hydrogenation of 42 was ineffective, but the reduction of 22 under H2 generated [(tBu3SiO)2MoH]2 (52), and the addition of 2-butyne to 3 gave [(silox)2Mo]2 (μ:ɳ2ɳ2-C2Me2) (6), thereby implicating the existence of [(silox)2Mo]2 (12). The addition of (silox)H to Mo(NMe2)4 led to (silox)2Mo(NMe2)2 (7), but further elaboration of the core proved ineffective. The silanolysis of MoCI5 afforded (silox)2MoCI4 (8) and (silox)3 MoCI3 (9) as a mixture from which pure 8 could be isolated, and the addition of THF or PMe3 resulted in derivatives of 9 as (silox)2CI3MoL (L = THF, 10; PMe3, 11). Reductions of 11 and (silox)2WCI4 (15) in the presence of excess PMe3 provided (silox)2CI2MPMe3 (M = Mo, 12; W, 16) or (silox)2HW(ɳ2-CH2PMe2)PMe3 (14). While "(silox)2W(PMe3)2" was unstable with respect to W(IV) as 14, a reduction of 12 led to the stable Mo(II) diphosphine, (silox)2Mo(PMe3)2 (17). X-ray crystal structures of 10 (pseudo-Oh), 12 (square pyramidal), and 14 and 17 (distorted Td) are reported. Calculations address the diamagnetism of 12 and 16, and the distortion of 17 and its stability to cyclometalation in contrast to 14. |
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| Creator(s): | |
| Creation Date: | October 21, 2008 |
| Partner(s): |
UNT College of Arts and Sciences
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| Collection(s): |
UNT Scholarly Works
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| Usage: |
Total Uses: 67
Past 30 days: 4
Yesterday: 0
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| Creator (Author): |
Kuiper, David S.
Cornell University |
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| Creator (Author): |
Wolczanski, Peter T.
Cornell University |
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| Creator (Author): |
Lobkovsky, Emil B.
Cornell University |
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| Creator (Author): |
Cundari, Thomas R., 1964-
University of North Texas |
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| Publisher Info: |
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
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| Original Creation Date: | October 21, 2008 | |
| Description: | This article discusses four-coordinate Mo(II). Abstract: The reduction of [(tBu3SiO)2MoCI]2 (22) provided the cyclometalated derivative, (silox)2HMoMo(k-O,C-OSitBu2CMe2CH2)(silox) (3), and alkylation of 22 with MeMgBr afforded [(tBu3SiO)2MoCH3]2 (42). The hydrogenation of 42 was ineffective, but the reduction of 22 under H2 generated [(tBu3SiO)2MoH]2 (52), and the addition of 2-butyne to 3 gave [(silox)2Mo]2 (μ:ɳ2ɳ2-C2Me2) (6), thereby implicating the existence of [(silox)2Mo]2 (12). The addition of (silox)H to Mo(NMe2)4 led to (silox)2Mo(NMe2)2 (7), but further elaboration of the core proved ineffective. The silanolysis of MoCI5 afforded (silox)2MoCI4 (8) and (silox)3 MoCI3 (9) as a mixture from which pure 8 could be isolated, and the addition of THF or PMe3 resulted in derivatives of 9 as (silox)2CI3MoL (L = THF, 10; PMe3, 11). Reductions of 11 and (silox)2WCI4 (15) in the presence of excess PMe3 provided (silox)2CI2MPMe3 (M = Mo, 12; W, 16) or (silox)2HW(ɳ2-CH2PMe2)PMe3 (14). While "(silox)2W(PMe3)2" was unstable with respect to W(IV) as 14, a reduction of 12 led to the stable Mo(II) diphosphine, (silox)2Mo(PMe3)2 (17). X-ray crystal structures of 10 (pseudo-Oh), 12 (square pyramidal), and 14 and 17 (distorted Td) are reported. Calculations address the diamagnetism of 12 and 16, and the distortion of 17 and its stability to cyclometalation in contrast to 14. |
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| Degree: |
Department:
Chemistry
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| Note: |
Reprinted with permission from Inorganic Chemistry. Copyright 2008 American Chemical Society. |
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| Physical Description: |
12 p. |
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| Language(s): | ||
| Subject(s): |
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| Keyword(s): | molybdenum | tungsten | |
| Source: | Inorganic Chemistry, 2008, Washington DC: American Chemical Society, pp. 10542-10553 | |
| Partner: |
UNT College of Arts and Sciences
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| Collection: |
UNT Scholarly Works
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| Resource Type: | Article | |
| Format: | Text | |
| Rights: |
Access:
Public
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| Citation: |
Publication Title: Inorganic Chemistry
Volume: 47
Issue: 22
Page Start: 10542
Page End: 10553
Pages: 12
Peer Reviewed: Yes
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